Geographical traceability of Italian white truffle (Tuber magnatum Pico) by the analysis of volatile organic compounds

Results are presented that were obtained on the geographic traceability of the white truffle Tuber magnatum Pico. Solid-phase microextraction coupled to gas chromatography/mass spectrometry (SPME-GC/MS) was employed to characterize the volatile profile of T. magnatum white truffle produced in seven geographical areas of Italy. The main components of the volatile fraction were identified using SPME-GC/MS. Significant differences in the proportion of volatile constituents from truffles of different geographical areas were detected. The results suggest that, besides genetic factors, environmental conditions influence the formation of volatile organic compounds. The mass spectra of the volatile fraction of the samples were used as fingerprints to characterize the geographical origin. Next, stepwise factorial discriminant analysis afforded a limited number of characteristic fragment ions that allowed a geographical classification of the truffles studied.     

Direct screening and confirmation of priority volatile organic pollutants in drinking water

A screening tool was proposed for the rapid detection of eight priority volatile organic pollutants according to European standards in drinking water. The method is based on the direct coupling of a headspace sampler with a mass spectrometer, using a chromatographic column heated to 175 degrees C as an interface. The water sample was subjected to the headspace extraction process and the volatile fraction was introduced directly into the mass spectrometer, without prior chromatographic separation, achieving low detection limits (0.6-1.2 ng/ml) for all compounds. The mass spectrum resulting from the simultaneous ionization and fragmentation of the mixture of molecules constitutes the volatile profile of each sample. An appropriate chemometric treatment of these signals permitted them to be classified, on the basis of their volatile composition, as contaminated or uncontaminated with respect to the legally established concentration levels for these compounds in drinking water, and providing no false negatives. A conventional confirmation method was carried out to analyze positive water samples by using the same instrumental setup as in the screening method, but using an appropriate temperature program in the chromatographic column to separate, identify and quantify each analyte.     

Fermentation condition outweighed truffle species in affecting volatile organic compounds analyzed by chromatographic fingerprint system

The influences of fermentation conditions and truffle species (i.e., Tuber melanosporum, Tuber sinense, Tuber indicum, and Tuber aestivum) on the volatile organic compounds (VOCs) originated from truffle fermentation mycelia were studied by using chromatographic fingerprint system for the first time. Gas chromatography combined with statistical methods including similarity analysis and hierarchical cluster analysis was applied to develop chromatographic fingerprint system for truffle VOCs evaluation. Fermentation conditions affected the VOCs from truffle fermentation mycelia much more significantly than truffle species. This indicated that it is possible to adjust the aroma of truffle fermentation mycelia similar with the natural fruiting-body through the control of fermentation process.     

Rapid white truffle headspace analysis by proton transfer reaction mass spectrometry and comparison with solid-phase microextraction coupled with gas chromatography/mass spectrometry

The gastronomic relevance and high price of white truffle are related mainly to its unique aroma. Here we evaluate, for the first time, the possibility of characterizing in a rapid and non-destructive way the aroma of white truffles based on proton transfer reaction mass spectrometry (PTR-MS). We indicate that anonymous PTR-MS fingerprinting allows sample classification and we also compare qualitatively and quantitatively PTR-MS data with measurements made by solid-phase microextraction gas chromatography (SPME-GC) of the same samples under the same conditions. PTR-MS fragmentation data of truffle-relevant compounds are also published here for the first time. Most of the sulfur-containing compounds detected by GC and relevant for white truffle aroma have a high positive correlation with single PTR-MS peaks. Our work indicates that, after preliminary comparison with GC data, PTR-MS is a new tool for the rapid, quantitative and non-invasive characterization of white truffle by direct headspace injection without any pre-concentration.     

固相微萃取-气相色谱/同位素质谱法测定水中挥发性有机物单体碳同位素

建立了采用75μm碳分子筛/聚二甲基硅氧烷(CAR-PDMS)纤维的固相微萃取-气相色谱/同位素质谱联用方法测定水中挥发性有机污染物碳同位素。使用浸入式固相微萃取和顶空固相微萃取方法进行实验确定在低浓度条件下最佳δ13C测试方法。通过使用顶空固相微萃取前处理技术进行单体同位素分析分析灵敏度更高,应用CSIA技术对1,2-二氯乙烯,三氯乙烯,四氯化碳进行单体同位素分析,方法的检出限为70μg/L,与样本的标准偏差小于0.3‰。该法适用于水体中微量挥发性有机污染物的同位素组成测定。     

Determination of specific volatile organic compounds synthesised during Tuber borchii fruit body development by solid-phase microextraction and gas chromatography/mass spectrometry

Fruit body development is a particular phase of the Tuber life cycle, characterised by the aggregation of different types of hyphae, i.e., vegetative hyphal cells and highly specialised reproductive hyphae (asci). In order to identify the volatile organic compounds (VOCs) produced in different stages of the Tuber borchii ripening fruit body, solid-phase microextraction with gas chromatography and mass spectrometry was used. The volatile organic compounds were extracted using a DVB/CAR/PDMS 50/30 microm fiber placed for 10 min at room temperature in the truffle headspace. The results obtained reveal 49 compounds each of which was present only in a particular stage of maturation. 1-octen-3-ol, aromadendrene, alpha-farnesene and other terpenoid compounds were of particular interest, and their possible biological roles are discussed. The production of aromadendrene in the completely unripe fruit body suggests the existence of communication events in the early stage of ascomata formation between the fungus and the host plant. alpha-Farnesene could represent a chemotactic attractant to saprophytic organisms in order to disperse the fungal spores in the environment. The identification of the VOCs produced by truffles during their maturation could give information about the processes underlying this phase of Tuber life cycle.     

顶空气相色谱法测定化妆品中15种挥发性有机溶剂残留

建立了化妆品中15种挥发性有机溶剂残留的顶空气相色谱测定方法。样品经60 ℃、30 min静态顶空后,采用气相色谱-氢火焰离子化检测器进行检测,外标法定量。加标回收试验结果表明: 15种挥发性有机溶剂残留平均回收率为62.8%～116%,相对标准偏差均小于5%。方法的检出限为0.09～0.68 mg/kg。该方法可有效克服基体干扰,一次进样可同时分离和测定化妆品中15种挥发性有机溶剂,准确灵敏,简单快速,适用于化妆品中挥发性有机溶剂残留的检测。     

Headspace solid-phase microextraction combined with GC×GC-TOFMS for the analysis of volatile compounds of Coptis species rhizomes

In this study, the investigation of the volatile compounds of dried rhizomes of Coptis chinensis Franch, C. deltoidea C. Y. Cheng et Hsiao, and C. teeta Wall was carried out to complete the chemical composition of these valuable natural products. Volatile profiles were established and compared after headspace solid-phase microextraction (HS-SPME) using a polydimethylsiloxane/divinylbenzene (PDMS/DVB, 65 μm) fibre coupled to comprehensive 2D gas chromatography time-of-flight mass spectrometry (GC×GC-TOFMS). Analyses were performed and compared on two column-phase combinations (non-polar/polar and polar/non-polar). The majority of the identified compounds eluted as well-separated (pure) components as a result of high-resolution capability of the GC×GC method, which significantly reduces co-elution. Therefore, this increases the likelihood that pure mass spectra can be obtained. More than 290 volatile and semi-volatile organic compounds were tentatively characterized by means of GC×GC in tandem with TOFMS detection. Improved result interpretations were obtained in terms of compound classification based on the organized structure of the peaks of structurally related compounds in the GC×GC contour plot. These compounds are distributed over the chemical groups of hydrocarbons, acids, alkenes, alkynes, aldehydes, ketones, alcohols, esters, furans, and terpenoids. Among all the chemical groups, terpenoids present the higher number of identified compounds (44), alkenes (41), and aldehydes and ketones (28). This study completed the volatile phytochemical analysis of the headspace composition of various Coptis species rhizomes, and should serve as a means to identify the difference between the rhizomes and may also be useful to confirm individual species based on their volatile chemical profile.     

Magnetic nanoparticles used in headspace extraction coupled with DSI-GC-IT/MS for analysis of VOCs in dry Traditional Chinese Medicine

A novel magnetic method using polystyrene modified magnetic nanoparticles to perform thermoheadspace extraction was successfully developed for extraction and preconcentration of volatile organic components in dry Traditional Chinese Medicine(TCM) based on gas chromatography-ion trap/mass spectrometry with a Chromato Probe direct sample introduction device. The dried fruit of Amomum testaceum Ridl. was used as the object TCM. The optimum parameters of headspace magnetic solid-phase extraction were investigated, in which desorption solvent ethyl acetate played a key role in this method,and the headspace extraction temperature of 90℃ and the headspace extraction time of 15 min finally decided. Headspace solid-phase microextraction method was also used to analyze volatile compounds in the TCM to compare with the proposed method. The results show that 60 components were identified totally by two methods; most of the low boiling point chemical compounds are isolated by this new method. In this work, an environmental-friendly and cheap analytical method was established, and a new approach to analyze volatile compounds in dry Traditional Chinese Medicine was also provided.     

Study of volatile compounds from the radiosterilization of solid cephalosporins

The use of γ-rays is a promising method to sterilize thermosensitive drugs. Although radiosterilization does not modify drugs activity, this mode of sterilization produces new radiolytic products. This study is devoted to the analysis of volatile compounds which may induce a modification of odour. The volatile compounds produced by radiolysis of cefotaxime, cefuroxime and ceftazidime, three cephalosporins, were analyzed by gas chromatography with headspace sampling. They were detected and identified by mass and infrared spectrometry. An explanation of their origin is proposed.     

Monitoring of headspace total volatile basic nitrogen from selected fish species using reflectance spectroscopic measurements of pH sensitive films

The release of amines from decomposing fish such as trimethylamine (TMA), dimethylamine (DMA) and ammonia, collectively known as total volatile basic nitrogen (TVB-N), are in high enough concentrations in headspace to be monitored by a colour change in a pH-sensitive sensor. A method developed here uses a pH indicator dye physically trapped in a cellulose polymer film to respond to the headspace TVB-N released from selected fish species during spoilage. Two species were selected for analysis on the basis of economic importance and the levels of volatile amines released were followed with time using uv/vis reflectance spectroscopic measurements. The results show that there is a significant increase in the TVB-N content in the headspace of fish samples after an incubation period of 8-12 h for cod and 12-15 h for orange roughy.     

Characterization of the volatile fraction emitted by phloems of four pinus species by solid-phase microextraction and gas chromatography-mass spectrometry

Pine forests constitute some of the most important renewable resources supplying timber, paper and chemical industries, among other functions. Characterization of the volatiles emitted by different Pinus species has proven to be an important tool to decode the process of host tree selection by herbivore insects, some of which cause serious economic damage to pines. Variations in the relative composition of the bouquet of semiochemicals are responsible for the outcome of different biological processes, such as mate finding, egg-laying site recognition and host selection. The volatiles present in phloem samples of four pine species, P. halepensis, P. sylvestris, P. pinaster and P. pinea, were identified and characterized with the aim of finding possible host-plant attractants for native pests, such as the bark beetle Tomicus piniperda. The volatile compounds emitted by phloem samples of pines were extracted by headspace solid-phase micro extraction, using a 2cm 50/30mm divinylbenzene/carboxen/polydimethylsiloxane table flex solid-phase microextraction fiber and its contents analyzed by high-resolution gas chromatography, using flame ionization and a non polar and chiral column phases. The components of the volatile fraction emitted by the phloem samples were identified by mass spectrometry using time-of-flight and quadrupole mass analyzers. The estimated relative composition was used to perform a discriminant analysis among pine species, by means of cluster and principal component analysis. It can be concluded that it is possible to discriminate pine species based on the monoterpenes emissions of phloem samples.     

Quantification of volatile compounds in the headspace of aqueous liquids using selected ion flow tube mass spectrometry

We describe a method by which the concentrations of volatile compounds in the headspace of their dilute aqueous solutions in sealed containers can be determined using on-line selected ion flow tube mass spectrometry (SIFT-MS). Thus, the changing number density of the molecules of the volatile compound in the carrier gas of the SIFT-MS instrument is described in terms of its changing flow rate as the pressure in the sealed container decreases during the sampling procedure. It is shown that the best analytical procedure is to determine the mean concentration of the trace gas in the liquid headspace over a given sampling time and relate this to the required concentration, which is the initial equilibrium concentration established before the pressure in the sealed container reduces significantly. To test the validity of this analytical approach, the headspace concentrations of acetaldehyde, ethanol and acetone above aqueous solutions of known concentrations have been determined. Hence, the Henry's Law constants for these compounds have been determined and found to agree with the published values. The confirmation of the quality of this sampling methodology combined with SIFT-MS for the analysis of volatile compounds in liquid headspace paves the way for the rapid analyses of biological liquids such as urine and serum for clinical diagnosis and physiological monitoring.     

Analysis of the volatile compounds in Senecio scandens Buch-Ham by gas chromatography-tandem mass spectrometry based on diversified scan technologies

Static headspace gas chromatography-tandem mass spectrometry was used to identify volatile compounds from Senecio scandens Buch-Ham. The elemental composition of compounds was confirmed by exploiting the tandem mass spectra of isotopic peaks from the precursor ion. Some isomers were well distinguished by the diversified scan technologies of tandem mass spectrometry (MS/MS). The MS/MS included a product ion scan, a precursor ion scan and a neutral loss scan. The results showed that 46 volatile compounds were completely identified, and the great of majority compounds were α-pinene (11.93%), n-caproaldehyde (9.02%) and dehydrosabinene (6.22%). This qualitative method is convenient and accurate and can be considered as a complementary identification method for the qualitative analysis of volatile compounds in complex samples.     

Determination of microbial volatile organic compounds from Staphylococcus pasteuri against Tuber borchii using solid-phase microextraction and gas chromatography/ion trap mass spectrometry

The mycelium of Tuber borchii Vittad., a commercial truffle species, is used as a model system for in vitro ectomycorrhizal synthesis, infected seedling production and biotechnological applications. Our fungal cultures were accidentally contaminated with a Staphylococcus pasteuri strain, showing a strong antifungal activity against T. borchii mycelium. In order to identify the antifungal volatile agents produced by S. pasteuri, solid-phase microextraction (SPME) with gas chromatography and mass spectrometry (GC/MS) was used. Using this method 65 microbial volatile organic compounds (MVOCs), synthesized by this bacterium in either single or in fungal-bacterial dual culture, were identified. SPME combined with GC/MS may be a useful method for the determination of MVOCs involved in the antifungal activity. These results showed that bacteria with unusual biological activities could be a major problem during large-scale production of inoculum for truffle-infected seedling.     

Identification of volatile basic components in tobacco by headspace liquid-phase microextraction coupled to matrix-assisted laser desorption/ionization with Fourier transform mass spectrometry

A method incorporating headspace liquid-phase microextraction (HS-LPME) coupled to matrix-assisted laser desorption/ionization (MALDI) with Fourier transform mass spectrometry (FTMS) was established to analyze volatile basic components in tobacco. The sample preparation volume for MALDI-MS was compatible with the volume of the solvent microdrop in the HS-LPME procedure. The pH and the polarity of the solvent for HS-LPME were adjusted by choice of the MALDI matrix and matrix additive. Based on the elemental composition and tandem mass spectrometry information, 25 volatile nitrogenous compounds in tobacco were detected and identified. The approach is fast and sensitive, and has the potential for automation for high-throughput analysis. This approach offers an alternative method for analysis of trace volatile organic compounds in complex samples.     

Quality assessment of liquid pharmaceutical preparations by HSS-GC-FID

A new headspace gas chromatographic method with flame ionization detection (HSS-GC-FID) was developed and validated for the determination of methanol as the main volatile impurity present in ethanolic pharmaceutical preparations. The use of static headspace sampling minimized the interference of other volatile matrix components and provided satisfactory results in purity assessment of different complex samples. The developed procedure revealed to be rapid, sensitive, reproducible and accurate. The detection and quantification limits of methanol were 0.0003 and 0.0011% (v/v), respectively, and were sufficiently low to enable the estimation of organic volatile impurity according to the ICH guideline as well as the examination of methanol limit specified in European Pharmacopoeia for liquid pharmaceutical preparations. The proposed method was successfully applied to the analysis of diverse alcoholic herbal extracts and tinctures as well as ethanolic dermatological lotions.     

A New Cell for Single Sided Headspace Sampling and Evaluation of Barrier Function in Laminated Paperboard

A new cell for single sided headspace sampling has been developed for the analysis of volatile organic compounds from food packaging paperboard and laminated paperboard. The cell, which samples the volatile organic compounds over a selected surface, is useful for determining the barrier function of laminated paperboards with respect to volatile compounds. The analysis of volatile organic compounds is carried out by purge and trap capillary gas chromatography in combination with mass spectrometric detection and compound identification. The new sampling cell was constructed to facilitate specific analysis of organic compounds from only one side of a laminated paperboard. The construction and the operating principles of the new sampling device are described. The repeatability of the single sided headspace procedure was found to be quite good. Relative standard deviations of about 5–7% were obtained for the major compounds quantified in replicate headspace analyses of a laminated paperboard. The volatile compounds released from the inner side of a food packaging paperboard sample with different surface composition on the two sides were determined. The barrier function against volatile organic compounds of some laminated paperboards was investigated employing the new headspace cell.     

顶空气相色谱质谱法快速测定液体食品中的挥发性酸

建立了一种用于快速测定食品中挥发性有机酸的分析方法.利用顶空技术对样品进行前处理,并与气相色谱质谱联用,用离子选择对11种挥发性有机酸进行定量分析.在优化的实验条件下,方法线性关系良好,线性范围为0.20 ～5 mg/L.11种挥发性有机酸的相关系数均大于0.998 6,检出限为0.000 2 ～35.5 mg/L,比全扫描检出限低1 ～3个数量级.11种挥发性有机酸的回收率为93% ～99%,相对标准偏差均小于10%.该方法简便、快速、重复性好、定性定量准确,适于食品中挥发性有机化合物的检测.     

Low‐temperature headspace‐trap gas chromatography with mass spectrometry for the determination of trace volatile compounds from the fruit of Lycium barbarum L.

The total saccharides content of Lycium barbarum L. is very high, and a high temperature would result in saccharide decomposition and the emergence of a large amount of water. Moreover, the volatile compounds from the fruit of L. barbarum L. are rather low in concentration. Hence, it is difficult for a conventional headspace method to study the volatile compounds from the fruit of L. barbarum L. Since headspace‐trap gas chromatography with mass spectrometry is an excellent method for trace analysis, a headspace‐trap gas chromatography with mass spectrometry method based on low‐temperature (30°C) enrichment and multiple headspace extraction was developed to explore the volatile compounds from the fruit of L. barbarum L. The headspace of the sample was extracted in 17 cycles at 30°C. Each time, the compounds extracted were concentrated in the trap (Tenax TA and Tenax GR, 1:1). Finally, all the volatile compounds were delivered into the gas chromatograph after thermal desorption. With the method described above, a total of 57 compounds were identified. The identification was completed by mass spectral search, retention index, and accurate mass measurement.